Alkyl esters of alkoxy-acyloxy stearic acid



United States Patent ALKYL ESTERS OF ALKOXY-ACYLOXY STEARIC ACID Lyle E. Gast, John C. Cowan, and Howard M. Teeter, Peoria, 111., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application November 25, 1955 Serial No. 549,205

12 Claims. ('Cl. 252--56) (Granted under Title 35, U. S. Code (1952), see. 266) This invention relates to new chemical compounds, wherein the stearic= namely, alkyl esters of stearic acid acid nucleus contains an alkoxy substituent and an :acyloxy substituent. It relates further to novel lubricating compositions comprising our novel chemical compounds, which possess low pour points and other advantageous characteristics as lubricants. The invention also includes processes wherein the said compounds are employed as lubricants. Further aspects of the invention will be evident from the following description.

The novel compounds have the following general formula:

in which R is an alkyl group of 1 to 8 carbon atoms, and the other Ris anacyl group of a lower aliphatic carboxylic acid.

The foregoing compounds possess exceedingly low pour points, falling generally below -50"F., and possess viscosities at 100 F. ranging generally from 15 to 30 centistokes andat210" F. from 3 to centistokes. The A. S. T. M. slopes vary from about 0.720 to about 0.780.

The new compounds may be prepared in a variety of ways, but we prefer to start with 9.10 epoxystearic acid, first preparing the alkyl alkoxyhydroxystearate, as for example by'the'methodof Swern, Billen and Scanlan, J. Am. Chem. Soc., 70, 1226 (1948); The method will be illustrated in the examples which follow. The washed and dried alkyl alkoxyhydroxystearate is then esterified with the appropriate acylation agent.

The method of Swern, Billen and Scanlan produces a compound in which the alkoxy (R) group is the same as the R group. The method may be modified or further extended by saponifying the alkyl alkoxyhydroxystearate and reesterifying to place a diiferent alkyl group in the position of R in the structural formula. By following these procedures outlined above and in the following examples, we may produce a compound in which the alkyl groups of the substituents R and R are the same or different.

The following examples illustrates the invention,

power to grant 2 EXAMPLE. I

A- mixture of 9,10 epoxystearic acid, methanol (4 ml. per g. of acid) and sulfuric acid (0.1 percent total charge) was heated for three hours on a steam bath.

T he sulfuric acid in the final reaction mixture was exactly neutralized with sodium hydroxide solution and excess methanol distilled at 30-40 mm. pressure. The product, methyl methoxyhydroxy stearate, was washed with water and dried; It was then dissolved in acetone (3 ml./ g. of. product), and'the solution. cooled to 20 C. and filtered to remove any alkyl dihydroxystearate that might have formed. Acetone was then removed by disdistillation, and the product was esterified by the procedure of Example III below.

EXAMPLE II The epoxy stearic acid in the foregoing example may be replaced by epoxidized soybean fatty acids, prepared by the method of Swern, J. Am. Chem. Soc., 67, 412 (1945); As an example, soybean fatty acids (neut. equiv.

283, iodine value 142) were epoxidized according to.

Swern with peracetic acid to yield an epoxidized product with neut. equiv. 339, iodine value 20; epoxy oxygen 4.0

percent. This product was treated with absolute methr anol and sulfuric acid in accordance with Example I, to produce the methyl methoxyhydroxy derivative consisting essentially of the stearate; OCH 14.93 percent.

EXAMPLE III A mixture of methyl methoxyhydroxy stearate, prepared in Example I; (lumole), propionic anhydride 14.7 moles) and propionyl chloride (0.35 mole) was heated on the steam bath for three hours. At the end of the reaction, excess propionating agents were distilled off at reduced pressure and the product was washed with water, washed again with sodium bicarbonate solution, and finally with water. The properties of the product, methyl, methoxypropionoxy stearate are found in the table.

In a manner similar to the above, other alkylor alkylacyl groups may be placed in the positions indicated in the general formula above. For example, the methyl methoxy hydroxystearate used in Example Iii may be substituted by isopropyl methoxyhydroxy stearate, and then propionated as in the example.

It is to be understood that the specific methods of acylation discussed above are not intended to be limiting on this invention, but are described herein only for the purposes of illustration.

A number of representative compounds in accordance with the foregoing examples, and their properties are tabulated below.

The-terms high melting and low melting 9,10-dihydroxystearic acid refer to two distinct diastereoisomeric mixtures of 9,10-dihydroxystearic acids. The high melting form is sometimes referred to as the erythro form, and the low melting form may similarly be called the three form. In high-melting 9,10-dihydroxystearic acid the two hydroxyl groups have the same spatial configuration as the two central hydroxyl groups in the fourcarbon-atom sugar, erythrose. The low-melting 9,10dihydroxy stearic acid is similarly related to the sugar threose.

The term 9(10), l2(l3)-dihydroxy stearic acid refers to a mixture of dihydroxystearic acids derived from linoleic acid. This mixture contains 9,12-, 9,13-, 10,12-, and 10,13-dihydroxystearic acids, but the proportion in which each is present in the mixture is not known.

were prepared Table I DERIVATIVES F ALKYL 9(10), (9) DIHYDROXYSTEARATEB d 4 74380 92 v 055355850 m 924352H33 uwunfim mm 0 OLLLLLLLL 0 g 4 111111111 0 T .w 60 m mm T 888829888 3 m m .1 .011 m 333323333 M 111111111 S S 8 t 0 1111111111 E S r \l) e B i DJMM (1. 0 w 502410495 n W 0m- 7m wmmm 0 50108 70875 .m r 1 20807%58965 r t 2 omooad d omnmnmad i 3 W 557755205 fi O M w WM 522863294 n w wmwmwnmmw m ES m 00550850329 5 7 7 55 0 1 IIINZIUHWflNM d 185019181758 0 0 0 L0L0 0 0 0 0 0 0694485100 0 t 3 Fl2666667756 N wa 0 P P 60 w 030006 J... showin Mm nmnwmwmmmmm 00000000000 Mfi 00000000000 0 425A 8334423 s MMMMMMMMMQ n h .s W 80212182080 1 m 11111 11 1 1 a "m? 0 0710450003 w tt vmm is. m wnw w Eh 2 Z wflw W- lllllllmmm ornrmoounw mm r 0 WW mm 0 0. d 0. C 0 M ESEBBBZEZWY R M u HHHHHH HIXW C R 2222: 2E CCCCCCCCCWM d eh V 7 7NW m 0 azaasmm m m m F P HHHHH zi w w 433393333 0 CCCCCCCnn D. m D 1 041194.7 m1 S n 0122410 2 22229-2222 o n o N M u x. m E x E u 3 1 a Not distilled.

Derivative of methyl esters of soybean fatty acids.

We claim:

1. A compound having the following structur mula:

9. A process comprising lubricating parts with. the compound of claim 3.

ricating parts with the 10. A process comprising lub compound of claim 4.

11. A process comprising lubricating parts with the compound of claim 5.

OR OR By 31 45 m on m .1 w t 2 S m h y m m m P 0] g .m E Z M MT C A .1 e r P b m U S 1 eE g T u .m H A .m i T I d S P e a m6 Dflfl O EI C m a T m an e m GM e0 m mf r. I 0 m P B 90 n R 41 Au w. no. u m 0 22 c 0 5 n r e ow n w. bww o P Mal L. m CC M P 00 a t. S f e omo m L t y 1 p 1E p U 1 1 0 m0 R C m r nip 8 ob 0 I .1 S fi l wP o a WP r 6 m m .1 o R.m mom m ae .1 .1r1 11 mh m y W iCm m 1 Y Me O O n a mco .l h u d O D .m em n .m h amn. K mwlom M m mm mh 1 t m. h S S a T 1 R wmm m w fmmnu oaaa R o 4. The compound of claim 1 in which R is ethyl, one 2,652,411 Teeter et a1. Sept. 15, 1953 R is ethyl and the other R is propionyl.

OTHER REFERENCES Chikamori: .Synthesis of Derivativ Stearic Acid, J. Chem. Soc. Japan.

e wmmm s fl a h mm D J t c O m am 72, pp. 747-8 (1951) (article in Japanese) (av at Army Medical Library, Washington, D

abstract in Chem. Ab. 46, 11108g).

e e e n H o o m m a w .w .m m I R P R h h 2 1C. wmflfi wflm m C21 n .m n .B Su 1 1 mmmR Mehr nWCQv-H fo mmPL e m dh e m tH C.1 H d w t h 3 m m m C... 01 0 00 ycl P YP eo n rht u HPT m ..m .w m R R C UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Lyle Eu Gast et a1,

Column 1, line 41, after "atoms, insert on of from 1 to 8 carbon atoms column 3, line 43,

the formula, for "0012 read ---COOR' m e R is an alkyl radical right-hand portion of Signed and sealed this 9th day of June 1959.

(SEAL) Attest:

KARL l'Lv AXLINE ROBERT C. WATSON Attesting Ofiicer Commissioner of Patents 

1. A COMPOUND HAVING THE FOLLOWING STRUCTURAL FORMULA:
 7. A PROCESS OF COMPRISING LUBRICATING PARTS WITH THE COMPOUND OF CLAIM
 1. 